US2977324A - Catalysts - Google Patents
Catalysts Download PDFInfo
- Publication number
- US2977324A US2977324A US743468A US74346858A US2977324A US 2977324 A US2977324 A US 2977324A US 743468 A US743468 A US 743468A US 74346858 A US74346858 A US 74346858A US 2977324 A US2977324 A US 2977324A
- Authority
- US
- United States
- Prior art keywords
- catalyst
- thallium
- naphthalene
- vanadyl
- vanadate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims description 59
- 238000000034 method Methods 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 18
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 17
- 229910052716 thallium Inorganic materials 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 229910010293 ceramic material Inorganic materials 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 3
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 42
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 25
- -1 vanadyl vanadate Chemical compound 0.000 description 21
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 18
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 18
- 125000005287 vanadyl group Chemical group 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- DASUJKKKKGHFBF-UHFFFAOYSA-L thallium(i) carbonate Chemical compound [Tl+].[Tl+].[O-]C([O-])=O DASUJKKKKGHFBF-UHFFFAOYSA-L 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 150000002791 naphthoquinones Chemical class 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940076134 benzene Drugs 0.000 description 1
- LAMJEIALKQRYBY-BTJKTKAUSA-N benzoic acid;(z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)C1=CC=CC=C1 LAMJEIALKQRYBY-BTJKTKAUSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
Definitions
- This invention relates to catalysts which are particularly suitable for the oxidation of aromatic hydrocarbons to oxygen-containing organic compounds.
- the present invention provides catalysts the use of which does not lead to the combustion of a substantial part of the starting material to carbon oxides and in consequence enables the oxidation process to be relatively easily controlled.
- catalysts suitable for the oxidation of aromatic hydrocarbons to oxygencontaining compounds are produced by a process comprising the steps of bringing a molten catalytic material com prising a vanadyl vanadate, as hereinafter defined, into contact with particles of a porous heat-resistant solid and allowing the product to cool, whereby there is obtained a catalyst comprising the support impregnated with solid vanadyl vanadate.
- vanadyl vanadate as used in this specification means a single solid phase or a mixture'of solid phases, produced by the processes hereinafter disclosed, each phase containing at least one of the metals thallium, silver, potassium, sodium, lithium or rubidium, to gether with oxides of vanadium, in which at least a part of the vanadium atoms have a valency of from.2 to 4. It should be noted that alternative names exist for vanadyl vanadates. They are, for example, also known as vanadico-vanadates or hypovanadato-vanadates.
- the preferred catalysts provided by thepresent invention are supported potassium vanadyl vanadate and supported thallium vanadyl vanadate. In these, the
- M20 1 V205 molar ratio (where M is potassium or thallium) may be within the range of 0.00l:l to 0.321 but is conveniently ofthet order of 0.05:1.
- Supports suitable for use in producing catalysts of the present invention are, for example, corundum, silica, silicon carbide or firebrick. In general, any high-melting porous ceramic material is suitable providingthat this does not contain injurious constituents.
- the process of the present invention may be carried out by fusing together vanadium pentoxide and the appropriate salt, for example, a potassium or thallium salt, preferably potassium carbonate or thallium carbonate.
- the appropriate salt for example, a potassium or thallium salt, preferably potassium carbonate or thallium carbonate.
- the molten material may then be cooled, this being accompanied by the evolution of oxygen and the formation of the desired vanadyl vanadate.
- This vanadyl vanadate is then melted again and particles of the support, graded to the desired size, are introduced and then quick 1y withdrawn to just above the surface of the molten ICC
- the support may be dipped into the melt before the evolution of oxygen and the formation of vanadyl vanadate, so that the oxygen evolved during the solidification and formation of vanadyl vanadate assists the'formation of. a porous .vanadyl vanadate structure within the pores of the support.
- the support may be impregnated with soluble salts of .vanadium pentoxide and the other metal to be present, for example, thallium nitrate, and the impregnated support may then be calcined so that the vanadyl vanadate is formed within the pores of the support.
- Catalysts produced by the process of the present invention are extremely hard and rugged. These properties are advantageous in either fixed bed or fluidised bed operations. In fixed bed operations the lower part of the bed can more readily withstand the weight of the upper part and in consequence crushing of the lower part of the catalyst bed, with concomitant pressure drop, does not quence new catalyst charges are required less frequently.
- the catalysts produced by the process of the present invention may be tumbled before use in orderto remove. any vanadyl vanadate adhering to the external surface.
- the catalysts are preferably employed in the form of particles or pieces which have sizes within a r'elativ'ely narrow range. If it is desired to operate with the catalyst in a very finely divided form, the particles's hould preferably be capable of retention by a sieve, but able to pass a sieve. If a catalyst in the form of larger granules is preferable, these granules may conveniently grade between 4;" and A a i
- the catalysts of the present invention are activated by operating for the first few hours at a temperature higher than that at which it is ultimately desired to 'work. For example, in the oxidation of naphthalene to phthalic anhydride, initial operation at 450 C. is'advantageous;
- the oxidation of naphthalene to phthalic anhydride is conveniently carried out at a temperature of the order of 425-450", C., while the oxidation of ortho-xylene to phthalic anhydride is conveniently carried out at sitess of 450-500" C.
- Compounds other than aromatic hydrocarbons may be oxidised using the catalysts of the present invention. They include, for example, paraffins and olefines, each of which must contain at least three carbon atoms; aldehydes, which yield carboxylic acids, and ketones. These compounds are preferably oxidised at temperatures in the range of 250 C. to 500 C. Thus, on oxidising isobutene with air (air isobutcne volume ratio of 85:15) at 400 C., a product is obtained which comprises formaldehyde, acetic acid, glyoxal, propionic acid and methacrolein.
- Example 1 1.29 gm. of thallium carbonate and 10 gm. of vanadium pentoxide were ground together and fused. The melt was agitated for some time to ensure homogeneous mixing and then allowed to cool. During the cooling stage, oxygen was evolved. The thallium vanadyl vanadate thus formed was re-melted; particles of alpha alumina were dipped into the melt, quickly withdrawn and allowed to drain. The particles of alpha alumina employed in this process were of a size which enabled them to be retained by a A sieve but to pass a A sieve. The dip procedure was repeated until the alpha alumina was fully impregnated with thallium vanadyl vanadate.
- the weight of thallium vanadyl vanadate incorporated into the alpha alumina was between and The catalyst was tumbled for one hour to remove any excess vanadyl vanadate adhering to the external surfaces. After this treatment, the abrasion resistance of the catalyst mass became similar to that of the support.
- Example 2 mls. of a catalyst comprising thallium vanadyl vanadate supported on alpha alumina, prepared as described in Example 1, was charged to a reactor and an air-naphthalene mixture (air naphthalene volume ratio 20.3:1) was passed over it at a rate of 5,000 litres per hour per litre of catalyst-filled space, the catalyst being maintained at a temperature of 446 C.
- the amount of naphthalene converted was found to be 44.4% and the pass yield of phthalic anhydride was 33.5%.
- Example 3 Example 1 was repeated using 0.774 gm. of thallium carbonate and 10 gm. of vanadium pentoxide. As before, the catalyst produced contained between 5 and 10% of thallium vanadyl vanadate based on the weight of alpha alumina. The catalyst was again tumbled for 1 hour to remove any excess of thallium vanadyl vanadate adhering to the external surfaces, and after this treatment the abrasion resistance and strength of the catalyst mass were similar to those of the alpha alumina.
- This catalyst was tested by charging 20 ml. of it to a metal reactor and passing an air-naphthalene mixture, with an air naphthalene volume ratio of 20:1, over it at a space velocity of 5,000 litres per litre of catalystfilled space per hour.
- the temperature of the catalyst was maintained at 425 C. 84% of naphthalene was converted, the pass yield of phthalic anhydride being 54%.
- the pass yields of lay-products were:
- Example4 A catalyst was produced, exactly as described in Example 1, using 0.258 gm. of thallium carbonate and 10 gm. of vanadium pentoxide.
- This catalyst was tested exactly as described in Example '3 except that the temperature of operation was 450 C. 97% of the naphthalene was converted, the
- Example 5 A catalyst was produced from 0.774 gram of thallium carbonate and 10 gm. of vanadium pentoxide by the process identical with that used in Example 1. This catalyst was used in the oxidation of naphthalene, the conditions being identical with those employed in Example 2. 97% of naphthalene was converted, the pass yield of phthalic anhydride being 64%, and the pass yields of byproducts were:
- a second sample of catalyst was heated at 450 C., the air-naphthalene gas mixture being passed through as before.
- the temperature was lowered after 8 hours to 420 C.; at this temperature the conversion of the naphthalene was 84% and the pass yield of phthalic anhydride was 59%.
- the improvement resulting from the activation process is very noticeable.
- a catalyst activated as in the preceding paragraph at 450 C. was employed under the conditions described above for naphthalene oxidation at 400 C.
- the conversion of naphthalene was 65% and the pass yield of phthalic anhydride was 50%.
- the conversion of naphthalene was only 10% and the pass yield of phthalic anhydride was 3.3%.
- Example 7 1.36 grams of thallium carbonate and 10 grams of vanadium pentoxide were ground together and fused. The melt was allowed to cool. The thallium vanadyl vanadate thus formed was re-melted and fused on to alumina as described in Example 1. The dipping procedure was repeated until the catalyst contained 5% by weight of thallium vanadyl vanadate.
- a process for the production of an oxidation catalyst which consists essentially of (1) contacting particles of a porous, high-melting, heat-resistant ceramic material with a molten catalytic material consisting essentiallyof a vanadyl vanadate of a metal selected from the group consisting of thallium, silver, potassium, so-
- K 0 ZV205 molar ratio being within the range of 0.00l:1 to 0.3:1.
- a process for the production of an oxidation catalyst which consists essentially of (1) fusing together vanadium pentoxide with an inorganic salt of a metal selected from the group consisting of thallium, silver, potassium, sodium,'lithium and rubidium, (2) cooling the molten material to permit evolution of oxygen and the formation of the vanadyl vanadate of the said metal, (3) re-melting the said vanadyl vanadate, (4) introduc-- ing particles of a porous, high-melting, heat-resistant ceramic material, of the desired size into the melt, (5) thereafter withdrawing the said particles and allowing them to drain, and repeating these steps until the internal pore structure of said particles is coated with the said vanadyl vanadate.
- a process for the production of an oxidation catalyst which consists essentially of (1) fusing together vanadium pentoxide and an inorganic salt of a metal selected from the group consisting of thallium, silver, potassium, sodium, lithium and rubidium, (2) dipping into said melt particles of a porous, high-melting, heatresistant ceramic material of the desired size, (3) cooling the product thereby formed while permitting evolution of oxygen during the solidification and formation of the solid vanadyl vanadate of the said metal within the internal pores of said ceramic material.
- a process for the production of an oxidation catalyst which consists essentially of (l) impregnating a porous, high-melting, heat-resistant ceramic material with p a soluble salt of vanadium pentoxide and of a metal selected from the group consisting of thallium, silver,
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Description
United States Patent CATALYSTS Dennis Albert Dowden and Alexander Muirhead Ure Caldwell, Norton-on-Tees, England, assignors to 1mperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed June 20, 1958, Ser. No. 743,468
Claims priority, application Great Britain June 26, 1957 9 Claims. (Cl. 252-443) This invention relates to catalysts which are particularly suitable for the oxidation of aromatic hydrocarbons to oxygen-containing organic compounds.
Processes for the oxidation of organic compounds, especially hydrocarbons, in the vapour phase by m eans of oxygen-containing gases in the presence or absence of catalysts, such as vanadia, are well-known, but have not proved entirely satisfactory, primarily due to the difficulties in avoiding combustion to carbon oxides, and in preventing the highly exothermic process from getting out of control.
The present invention provides catalysts the use of which does not lead to the combustion of a substantial part of the starting material to carbon oxides and in consequence enables the oxidation process to be relatively easily controlled.
According to the present invention, catalysts suitable for the oxidation of aromatic hydrocarbons to oxygencontaining compounds are produced by a process comprising the steps of bringing a molten catalytic material com prising a vanadyl vanadate, as hereinafter defined, into contact with particles of a porous heat-resistant solid and allowing the product to cool, whereby there is obtained a catalyst comprising the support impregnated with solid vanadyl vanadate.
The term vanadyl vanadate as used in this specification means a single solid phase or a mixture'of solid phases, produced by the processes hereinafter disclosed, each phase containing at least one of the metals thallium, silver, potassium, sodium, lithium or rubidium, to gether with oxides of vanadium, in which at least a part of the vanadium atoms have a valency of from.2 to 4. It should be noted that alternative names exist for vanadyl vanadates. They are, for example, also known as vanadico-vanadates or hypovanadato-vanadates.
The preferred catalysts provided by thepresent invention are supported potassium vanadyl vanadate and supported thallium vanadyl vanadate. In these, the
M20 1 V205 molar ratio (where M is potassium or thallium) may be within the range of 0.00l:l to 0.321 but is conveniently ofthet order of 0.05:1. Supports suitable for use in producing catalysts of the present invention are, for example, corundum, silica, silicon carbide or firebrick. In general, any high-melting porous ceramic material is suitable providingthat this does not contain injurious constituents.
The process of the present invention may be carried out by fusing together vanadium pentoxide and the appropriate salt, for example, a potassium or thallium salt, preferably potassium carbonate or thallium carbonate.
7 The molten material may then be cooled, this being accompanied by the evolution of oxygen and the formation of the desired vanadyl vanadate. This vanadyl vanadate is then melted again and particles of the support, graded to the desired size, are introduced and then quick 1y withdrawn to just above the surface of the molten ICC Alternatively the support may be dipped into the melt before the evolution of oxygen and the formation of vanadyl vanadate, so that the oxygen evolved during the solidification and formation of vanadyl vanadate assists the'formation of. a porous .vanadyl vanadate structure within the pores of the support.
As yet another alternative, the support may be impregnated with soluble salts of .vanadium pentoxide and the other metal to be present, for example, thallium nitrate, and the impregnated support may then be calcined so that the vanadyl vanadate is formed within the pores of the support.
Catalysts produced by the process of the present invention are extremely hard and rugged. These properties are advantageous in either fixed bed or fluidised bed operations. In fixed bed operations the lower part of the bed can more readily withstand the weight of the upper part and in consequence crushing of the lower part of the catalyst bed, with concomitant pressure drop, does not quence new catalyst charges are required less frequently.
If desired, the catalysts produced by the process of the present invention may be tumbled before use in orderto remove. any vanadyl vanadate adhering to the external surface. V
The catalysts are preferably employed in the form of particles or pieces which have sizes within a r'elativ'ely narrow range. If it is desired to operate with the catalyst in a very finely divided form, the particles's hould preferably be capable of retention by a sieve, but able to pass a sieve. If a catalyst in the form of larger granules is preferable, these granules may conveniently grade between 4;" and A a i The catalysts of the present invention are activated by operating for the first few hours at a temperature higher than that at which it is ultimately desired to 'work. For example, in the oxidation of naphthalene to phthalic anhydride, initial operation at 450 C. is'advantageous;
stantially at the valueattained at 450 C.,' iusofarias phthalic anhydride productionfis concerned." Thereis;
however, less tendency at 425 C. than at 450 C. for m desirable combustion of the naphthalene to carbon o'xides and water.
The catalysts produced the process of the present invention maybe employed, for example, in .the' oxidation of toluene to benzoic acid; ortho-xylene ornaphtha= lene to phthalic anhydride; meta or para-di-isopropyl benzene to meta or para-di-isopropyl benzoic'acid; ben zene to maleic acid or maleic anhydride.
In general, the oxidation ,of aromatic "hydrocarbons i using catalysts produced by the process of the present in e n is op t d. at a empe a re he anse. o
Patented Mar. 28,
550 C., the optimum temperature depending upon the starting material to be oxidised. Thus, the oxidation of naphthalene to phthalic anhydride is conveniently carried out at a temperature of the order of 425-450", C., while the oxidation of ortho-xylene to phthalic anhydride is conveniently carried out at temperaturas of 450-500" C.
Compounds other than aromatic hydrocarbons may be oxidised using the catalysts of the present invention. They include, for example, paraffins and olefines, each of which must contain at least three carbon atoms; aldehydes, which yield carboxylic acids, and ketones. These compounds are preferably oxidised at temperatures in the range of 250 C. to 500 C. Thus, on oxidising isobutene with air (air isobutcne volume ratio of 85:15) at 400 C., a product is obtained which comprises formaldehyde, acetic acid, glyoxal, propionic acid and methacrolein.
Example 1 1.29 gm. of thallium carbonate and 10 gm. of vanadium pentoxide were ground together and fused. The melt was agitated for some time to ensure homogeneous mixing and then allowed to cool. During the cooling stage, oxygen was evolved. The thallium vanadyl vanadate thus formed was re-melted; particles of alpha alumina were dipped into the melt, quickly withdrawn and allowed to drain. The particles of alpha alumina employed in this process were of a size which enabled them to be retained by a A sieve but to pass a A sieve. The dip procedure was repeated until the alpha alumina was fully impregnated with thallium vanadyl vanadate. The weight of thallium vanadyl vanadate incorporated into the alpha alumina was between and The catalyst was tumbled for one hour to remove any excess vanadyl vanadate adhering to the external surfaces. After this treatment, the abrasion resistance of the catalyst mass became similar to that of the support.
A mixture of 21.2 grams of ortho-xylene vapour and 480 litres of air was passed over 50 mls, of the thallium vanadyl vanadate supported on alpha alumina prepared as described above. The catalyst bed occupied a 3" length of a reactor tube, 30" long and 1.25" in diameter, and was heated electrically. At an operating temperature of 500 C., ortho-xylene was converted to phthalic anhydride with a conversion of 64.1% and a pass yield of 35.5%.
Example 2 mls. of a catalyst comprising thallium vanadyl vanadate supported on alpha alumina, prepared as described in Example 1, was charged to a reactor and an air-naphthalene mixture (air naphthalene volume ratio 20.3:1) was passed over it at a rate of 5,000 litres per hour per litre of catalyst-filled space, the catalyst being maintained at a temperature of 446 C. The amount of naphthalene converted was found to be 44.4% and the pass yield of phthalic anhydride was 33.5%. The pass yield of ultimate conversion products, that is CO +CO+H O, was 2.6%.
For comparison, the same reaction was carried out using a catalyst comprising fused vanadium pentoxide supported on alpha alumina; conditions of operation were otherwise identical. The naphthalene conversion was 89% and the phthalic anhydride pass yield was 43.7%. The pass yield of ultimate oxidation products, that is CO +CO+H O, was 34.1%.
Example 3 Example 1 was repeated using 0.774 gm. of thallium carbonate and 10 gm. of vanadium pentoxide. As before, the catalyst produced contained between 5 and 10% of thallium vanadyl vanadate based on the weight of alpha alumina. The catalyst was again tumbled for 1 hour to remove any excess of thallium vanadyl vanadate adhering to the external surfaces, and after this treatment the abrasion resistance and strength of the catalyst mass were similar to those of the alpha alumina.
This catalyst was tested by charging 20 ml. of it to a metal reactor and passing an air-naphthalene mixture, with an air naphthalene volume ratio of 20:1, over it at a space velocity of 5,000 litres per litre of catalystfilled space per hour. The temperature of the catalyst was maintained at 425 C. 84% of naphthalene was converted, the pass yield of phthalic anhydride being 54%. The pass yields of lay-products were:
Percent Phthalic acid 0.1 Maleic acid 4 Benzoic acid 4 1:4 naphthaquinone 4 CO +CO+H O 19 In order to carry out a comparative experiment, alpha alumina was impregnated with a solution of vanadyl chloride and the product was calcined in steam. A catalyst was obtained which contained 6-7% by weight of By the process described earlier in this example, 20 ml. of this catalyst were used in the oxidation of naphthalene. The conditions employed were exactly the same as those previously given. 99.3% of the naphthalene was converted to phthalic anhydride, the pass yield of which was 49%. The pass yields of byproducts were:
Percent Phthalic acid 2.5 Maleic acid 7.0 Benzoic acid 2.5 1:4 naphthaquinone 0.2 CO +CO+H O 40.5
In particular it will be noted that the quantity of CO +CO+H O was more than twice the amount previously produced.
Example4 A catalyst Was produced, exactly as described in Example 1, using 0.258 gm. of thallium carbonate and 10 gm. of vanadium pentoxide.
This catalyst was tested exactly as described in Example '3 except that the temperature of operation was 450 C. 97% of the naphthalene was converted, the
pass yield of phthalic anhydride being 70%. The pass yields of by-products were:
Percent Phthalic acid 1 Maleic acid 8 Benzoic acid 4 1:4 naphthaquinone 2.5 CO +CO+H O 14 A comparative example was carried out exactly as described in Example 2. 99.5% of the naphthalene was converted, the pass yield of the phthalic anhydride being 40%. The pass yields of byproducts were:
Percent Phthalic acid 1.5 Maleic acid 7.0 Benzoic acid 2.5 1:4 naphthaquinone 0.2 CO +CO+H O 51 From these results it is evident that the quantity of CO +CO+H O was between 3 and 4 times as great when using a conventional catalyst.
Example 5 A catalyst was produced from 0.774 gram of thallium carbonate and 10 gm. of vanadium pentoxide by the process identical with that used in Example 1. This catalyst was used in the oxidation of naphthalene, the conditions being identical with those employed in Example 2. 97% of naphthalene was converted, the pass yield of phthalic anhydride being 64%, and the pass yields of byproducts were:
Percent Phthalic acid 0.1 Maleic acid Benzoic acid 2.5 1:4 naphthaquinone 3.5 CO +CO+H O 25 Example 6 Silver carbonate (0.104 gm.) and vanadium pentoxide gms.) were ground together and fused. The melt was agitated to ensure homogeneous mixing, and then allowed to cool. The silver vanadyl vanadate thus formed was re-melted. Particles of porous alpha alumina, capable of passing a sieve, but of being retained by a As" sieve, were dipped into the melt, quickly withdrawn and allowed to drain. This procedure was repeated five times, the internal pore structure of the support being impregnated in this way with silver vanadyl vanadate. The weight of silver vanadyl vanadate incorporated into the alpha alumina in this manner was 5%. This material was tumbled for 1 hour to remove any silver vanadyl vanadate adhering relatively loosely to the surface.
20 ml. of this catalyst were charged to a metal reactor and a mixture of air and naphthalene in a volume ratio of 20:1 was passed over the catalyst at a space velocity of 5,000 litres per litre of catalyst-filled space per hour. The catalyst was maintained at a temperature of 420 C. Of the naphthalene passed through the reactor, 78% was converted, the pass yield of phthalic anhydride being 46%.
A second sample of catalyst was heated at 450 C., the air-naphthalene gas mixture being passed through as before. The temperature was lowered after 8 hours to 420 C.; at this temperature the conversion of the naphthalene was 84% and the pass yield of phthalic anhydride was 59%. The improvement resulting from the activation process is very noticeable.
Similarly, a catalyst activated as in the preceding paragraph at 450 C. was employed under the conditions described above for naphthalene oxidation at 400 C. The conversion of naphthalene was 65% and the pass yield of phthalic anhydride was 50%. When using an unactivated catalyst at 400 C. the conversion of naphthalene was only 10% and the pass yield of phthalic anhydride was 3.3%.
Example 7 1.36 grams of thallium carbonate and 10 grams of vanadium pentoxide were ground together and fused. The melt was allowed to cool. The thallium vanadyl vanadate thus formed was re-melted and fused on to alumina as described in Example 1. The dipping procedure was repeated until the catalyst contained 5% by weight of thallium vanadyl vanadate.
30 ml. of this catalyst were charged to a reactor and i a gas mixture comprising 85 parts by volume of air and 15 parts by volume of isobutene was passed over it at a rate of 100 litres per hour. The catalyst was maintained at a temperature of 402 C. 32% of the isobutene underwent conversion. Of the converted material, 32% by weight consisted of useful oxygenated products.
We claim:
1. A process for the production of an oxidation catalyst which consists essentially of (1) contacting particles of a porous, high-melting, heat-resistant ceramic material with a molten catalytic material consisting essentiallyof a vanadyl vanadate of a metal selected from the group consisting of thallium, silver, potassium, so-
dium, lithium and rubidium, and (2) thereafter allowing the product to cool, whereby there is obtained a catalyst consisting essentially of the said ceramic material impregnated with the said solid vanadyl vanadate.
2. A process as claimed in claim 1 in which a potassium vanadyl vanadate catalyst is produced, the
K 0 ZV205 molar ratio being within the range of 0.00l:1 to 0.3:1. l
5. A process as claimed in claim 1 in which the catalyst has a size within a relatively narrow range extending from to for finely divided particles to A3" to 7 for granules.
6. The process of claim 1 including the final step of activating said oxidation catalyst by oxidizing naphthalene to phthalic anhydride with gaseous oxygen at a temperature of about 450 C. for a required period of up to 8 hours.
7. A process for the production of an oxidation catalyst which consists essentially of (1) fusing together vanadium pentoxide with an inorganic salt of a metal selected from the group consisting of thallium, silver, potassium, sodium,'lithium and rubidium, (2) cooling the molten material to permit evolution of oxygen and the formation of the vanadyl vanadate of the said metal, (3) re-melting the said vanadyl vanadate, (4) introduc-- ing particles of a porous, high-melting, heat-resistant ceramic material, of the desired size into the melt, (5) thereafter withdrawing the said particles and allowing them to drain, and repeating these steps until the internal pore structure of said particles is coated with the said vanadyl vanadate.
8. A process for the production of an oxidation catalyst which consists essentially of (1) fusing together vanadium pentoxide and an inorganic salt of a metal selected from the group consisting of thallium, silver, potassium, sodium, lithium and rubidium, (2) dipping into said melt particles of a porous, high-melting, heatresistant ceramic material of the desired size, (3) cooling the product thereby formed while permitting evolution of oxygen during the solidification and formation of the solid vanadyl vanadate of the said metal within the internal pores of said ceramic material.
.9. A process for the production of an oxidation catalyst which consists essentially of (l) impregnating a porous, high-melting, heat-resistant ceramic material with p a soluble salt of vanadium pentoxide and of a metal selected from the group consisting of thallium, silver,
potassium, sodium, lithium and rubidium, and (2) thereafter calcining the thus-impregnated ceramic material," thereby forming the vanadyl vanadate of said metal within the pores of said ceramic material.
References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
1. A PROCESS FOR THE PRODUCTION OF AN OXIDATION CATALYST WHICH CONSISTS ESSENTIALLY OF (1) CONTACTING PARTICLES OF A POROUS, HIGH-MELTING, HEAT-RESISTANT CERAMIC MATERIAL WITH A MOLTEN CATALYTIC MATERIAL CONSISTING ESSENTIALLY OF A VANADYL VANADATE OF A METAL SELECTED FROM THE GROUP CONSISTING OF THALLIUM, SILVER, POTASSIUM, SODIUM, LITHIUM AND RUBIDIUM, AND (2) THEREAFTER ALLOWING THE PRODUCT TO COOL, WHEREBY THERE IS OBTAINED A CATALYST CONSISTING ESSENTIALLY OF THE SAID CERAMIC MATERIAL IMPREGNATED WITH THE SAID SOLID VANADYL VANADATE.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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GB2977324X | 1957-06-26 |
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US2977324A true US2977324A (en) | 1961-03-28 |
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US743468A Expired - Lifetime US2977324A (en) | 1957-06-26 | 1958-06-20 | Catalysts |
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US3226338A (en) * | 1959-07-03 | 1965-12-28 | United Coke And Chemicals Comp | Vanadium pentoxide potassium pyrosulfate catalyst and method of preparation thereof |
US3870655A (en) * | 1972-01-31 | 1975-03-11 | Nippon Catalytic Chem Ind | Catalyst for the preparation of anthraquinone |
US3963645A (en) * | 1969-02-27 | 1976-06-15 | The Lummus Company | Supported metal oxides |
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US2157965A (en) * | 1937-06-28 | 1939-05-09 | Helmuth Reichhold | Process for producing phthalic anhydride |
US2485073A (en) * | 1946-02-01 | 1949-10-18 | California Research Corp | Hydrocarbon conversions |
US2698306A (en) * | 1951-05-05 | 1954-12-28 | O Hommel Company | Oxidation catalyst |
US2760906A (en) * | 1951-09-04 | 1956-08-28 | Exxon Research Engineering Co | Desulfurization of hydrocarbon oils with vanadium oxide catalyst in the presence of naphthenes |
US2809939A (en) * | 1954-11-18 | 1957-10-15 | American Cyanamid Co | Fluidized silica gel catalysts containing vanadium pentoxide and oxides of metals of group iii-b and iv-a |
US2824880A (en) * | 1953-04-10 | 1958-02-25 | Ciba Ltd | Process for the manufacture of anthraquinone from anthracene by catalytic oxidation |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US2016169A (en) * | 1932-04-27 | 1935-10-01 | Gas Light & Coke Co | Hydrogenation of carbonaceous materials |
US2157965A (en) * | 1937-06-28 | 1939-05-09 | Helmuth Reichhold | Process for producing phthalic anhydride |
US2485073A (en) * | 1946-02-01 | 1949-10-18 | California Research Corp | Hydrocarbon conversions |
US2698306A (en) * | 1951-05-05 | 1954-12-28 | O Hommel Company | Oxidation catalyst |
US2760906A (en) * | 1951-09-04 | 1956-08-28 | Exxon Research Engineering Co | Desulfurization of hydrocarbon oils with vanadium oxide catalyst in the presence of naphthenes |
US2824880A (en) * | 1953-04-10 | 1958-02-25 | Ciba Ltd | Process for the manufacture of anthraquinone from anthracene by catalytic oxidation |
US2809939A (en) * | 1954-11-18 | 1957-10-15 | American Cyanamid Co | Fluidized silica gel catalysts containing vanadium pentoxide and oxides of metals of group iii-b and iv-a |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US3226338A (en) * | 1959-07-03 | 1965-12-28 | United Coke And Chemicals Comp | Vanadium pentoxide potassium pyrosulfate catalyst and method of preparation thereof |
US3963645A (en) * | 1969-02-27 | 1976-06-15 | The Lummus Company | Supported metal oxides |
US3870655A (en) * | 1972-01-31 | 1975-03-11 | Nippon Catalytic Chem Ind | Catalyst for the preparation of anthraquinone |
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